US4034024A - Method of preparing trialkyl tetrathiophosphates - Google Patents
Method of preparing trialkyl tetrathiophosphates Download PDFInfo
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- US4034024A US4034024A US05/650,488 US65048876A US4034024A US 4034024 A US4034024 A US 4034024A US 65048876 A US65048876 A US 65048876A US 4034024 A US4034024 A US 4034024A
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- 238000000034 method Methods 0.000 title claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 5
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- -1 ethylcyclohexyl Chemical group 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000000654 additive Substances 0.000 abstract description 3
- 125000002723 alicyclic group Chemical group 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 9
- 238000004679 31P NMR spectroscopy Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 150000003568 thioethers Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910003944 H3 PO4 Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000007944 thiolates Chemical class 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 2
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007866 anti-wear additive Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
Definitions
- the present invention relates to a new and improved method of preparation of trialkyl tetrathiophosphates.
- R is selected from the group consisting of CH 3 , C 2 H 5 , n-C 4 H 9 , o-CH 3 C 6 H 4 , p-CH 3 C 5 H 4 and p-ClC 6 H 4 .
- reaction (2) trialkyl tetrathiophosphates are prepared in boiling benzene whereas triaryl tetrathiophosphates can only be obtained in boiling xylene.
- R is selected from the group consisting of CH 2 C 6 H 5 , C 6 H 5 , m--CH 3 C 6 H 4 .
- tetrathiophosphates include the reaction of thiophosphoryl chloride with either a thiol or a sodium thiolate and the reaction of phosphorus pentasulfide and thiols.
- R 1 and R 2 are the same or different and are selected from the group consisting of aliphatic groups having from 1 to about 18 carbon atoms and alicyclic of 5 to 6 carbons in the ring and the C 1 -C 4 alkyl substituted derivatives thereof.
- the aliphatic groups include C 1 -C 18 straight-chain or branched alkyl groups and the alicyclic groups include cycloalkyl of 5 to 6 carbons in the ring and the C 1 -C 4 alkyl substituted derivatives thereof.
- R groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclohexyl and cyclopentyl and the C 1 -C 4 alkyl substituted derivatives thereof.
- the method comprises contacting a dialkyl sulfide reactant of the formula:
- Reactants utilized in the process of the present invention can be employed in stoichiometric amounts, although an excess of either reactant can be used if desired.
- the process of the present invention is carried out at elevated temperature and at least at autogenous pressure and preferably at a pressure of between about 1 and 300 atmospheres. Temperatures of between about 150° to about 300° C. can be used though temperatures of about 180° C. to about 250° C. are preferred.
- trialkyl tetrathiophosphate products of the present invention are known and have utility as additives, agricultural chemicals, pharmaceutical chemicals and as intermediates in the preparation of other organophosphorus compounds.
- trialkyl tetrathiophosphates are used as anti-wear additives in lubricating oils and as additives to fuel for improving surface ignition control in engines operating in the Otto cycle.
- the products are known to have synergistic effects when used with certain pharmaceuticals and insecticides.
- the method of the present invention may conveniently be effected by introducing the individual reactants into a reaction zone; equipped with an agitation means (a rocker, vibrator or stirrer) for best results.
- an agitation means a rocker, vibrator or stirrer
- the reaction zone must be capable of withstanding elevated pressure.
- Pressure vessels such as metal bombs, autoclaves and the like or a vessel kept under an inert atmosphere, such as nitrogen, at a pressure sufficient to prevent the dialkyl sulfide from being lost by distillation are suitable for this purpose.
- the reaction is carried out under at least the autogenous pressure developed by the reactants at the reaction temperature.
- Pressures of up to 100 atmospheres above the autogenous pressure can also be used, but are less desirable due to the inconvenience of requiring a pressurization system.
- higher boiling dialkyl sulfides for example dioctyl sulfide, no pressure vessel is required.
- the reaction may be carried out in a continuous or batchwise system as desired.
- Reaction times vary over relatively wide ranges depending upon reaction temperature and the reactivity of the dialkyl sulfide. Generally, higher reaction temperatures require a shorter reaction time and low boiling dialkyl sulfides require longer reaction times than high boiling dialkyl sulfides. For example, dimethyl sulfide requires a longer reaction time than the longer chain dialkyl sulfides. Times of reaction can easily be determined by one skilled in the art. Typical reaction times are between 1 and about 24 hours. Preferred reaction times are between about 2 and about 12 hours.
- the products of the reaction are purified by conventional methods such as distillation, filtration, sublimation and extraction.
- the identification of products is achieved by conventional methods such as elemental analysis, gas chromatography, refractive index and nuclear magnetic resonance ( 31 P-nmr and H-nmr).
- example II was repeated at a lower reaction temperature and in a glass Carius tube as follows:
- example V was repeated at a lower temperature and in a glass Carius tube as follows:
- example VII was repeated at atmospheric pressure as follows:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Trialkyl tetrathiophosphates are prepared by contacting a dialkyl sulfide with phosphorus pentasulfide according to the following theoretical reaction scheme:
6R.sup.1 SR.sup.2 + P.sub.4 S.sub.10 → 4(R.sup.1 S).sub.x (R.sup.2
S)y P(S)
wherein x + y = 3; R1 and R2 are the same or different and are selected from the group consisting of aliphatic, having from 1 to about 18 carbon atoms, and alicyclic having 5 or 6 carbon atoms in the ring and the C1 -C4 alkyl substituted derivatives thereof. The contacting is effected under at least autogenous pressure at a temperature of from about 150° C. to 300° C. The compounds obtained are useful as additives in agricultural chemicals and as intermediates in preparation of other organophosphorus compounds.
Description
This is a continuation of application Ser. No. 514,525 filed Oct. 15, 1974, now abandoned.
1. Field of the Invention
The present invention relates to a new and improved method of preparation of trialkyl tetrathiophosphates.
2. The Prior Art
Tetrathiophosphates have been prepared in the prior art by reacting lead thiolates with thiophosphoryl chloride according to the following general reaction scheme:
Pb(SR).sub.2 + P(S)Cl.sub.3 → (RS).sub.3 P(S)+ R.sub.2 S.sub.2 + PbCl.sub.2 ( 2)
wherein R is selected from the group consisting of CH3, C2 H5, n-C4 H9, o-CH3 C6 H4, p-CH3 C5 H4 and p-ClC6 H4. Under reaction (2), trialkyl tetrathiophosphates are prepared in boiling benzene whereas triaryl tetrathiophosphates can only be obtained in boiling xylene.
Another reaction is observed for thiolates, namely:
Pb(SR).sub.2 + P(S)Cl.sub.3 → PbS+ R.sub.2 S.sub.2 + PCl.sub.3 ( 3)
wherein R is selected from the group consisting of CH2 C6 H5, C6 H5, m--CH3 C6 H4. These reactions are described in Phosphorus, R. A. Shaw and M. Woods, Vol. 1, Part 1, (Oxford, England, 1971) p. 42.
Other known methods of preparing tetrathiophosphates include the reaction of thiophosphoryl chloride with either a thiol or a sodium thiolate and the reaction of phosphorus pentasulfide and thiols.
In accordance with the present invention, there is provided a new method of preparing compounds of the formula:
(R.sup.1 S).sub.x (R.sup.2 S).sub.y P(S) I
wherein x+ y= 3; R1 and R2 are the same or different and are selected from the group consisting of aliphatic groups having from 1 to about 18 carbon atoms and alicyclic of 5 to 6 carbons in the ring and the C1 -C4 alkyl substituted derivatives thereof. The aliphatic groups include C1 -C18 straight-chain or branched alkyl groups and the alicyclic groups include cycloalkyl of 5 to 6 carbons in the ring and the C1 -C4 alkyl substituted derivatives thereof.
Exemplary R groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclohexyl and cyclopentyl and the C1 -C4 alkyl substituted derivatives thereof.
The method comprises contacting a dialkyl sulfide reactant of the formula:
R.sup.1 SR.sup.2 II
wherein R1 and R2 are as defined above, with phosphorus pentasulfide having the formula:
P.sub.4 S.sub.10. III
the following equation (1) is representative of the reaction:
6R.sup.1 SR.sup.2 + P.sub.4 S.sub.10 → 4(R.sup.1 S).sub.x (R.sup.2 S).sub.y P(S) (1)
where x+ y= 3. In the event that R1 and R2 are different, a mixed product results and thus x can be 0, 1, 2 or 3 and y can be 0, 1, 2 or 3 as long as the sum of x and y is equal to 3.
Reactants utilized in the process of the present invention can be employed in stoichiometric amounts, although an excess of either reactant can be used if desired.
The process of the present invention is carried out at elevated temperature and at least at autogenous pressure and preferably at a pressure of between about 1 and 300 atmospheres. Temperatures of between about 150° to about 300° C. can be used though temperatures of about 180° C. to about 250° C. are preferred.
The trialkyl tetrathiophosphate products of the present invention are known and have utility as additives, agricultural chemicals, pharmaceutical chemicals and as intermediates in the preparation of other organophosphorus compounds. For example, trialkyl tetrathiophosphates are used as anti-wear additives in lubricating oils and as additives to fuel for improving surface ignition control in engines operating in the Otto cycle. Also, the products are known to have synergistic effects when used with certain pharmaceuticals and insecticides.
The method of the present invention may conveniently be effected by introducing the individual reactants into a reaction zone; equipped with an agitation means (a rocker, vibrator or stirrer) for best results. When low boiling dialkyl sulfides are used, for example dimethyl sulfide, the reaction zone must be capable of withstanding elevated pressure. Pressure vessels such as metal bombs, autoclaves and the like or a vessel kept under an inert atmosphere, such as nitrogen, at a pressure sufficient to prevent the dialkyl sulfide from being lost by distillation are suitable for this purpose. The reaction is carried out under at least the autogenous pressure developed by the reactants at the reaction temperature. Pressures of up to 100 atmospheres above the autogenous pressure can also be used, but are less desirable due to the inconvenience of requiring a pressurization system. When higher boiling dialkyl sulfides are used, for example dioctyl sulfide, no pressure vessel is required. The reaction may be carried out in a continuous or batchwise system as desired.
Reaction times vary over relatively wide ranges depending upon reaction temperature and the reactivity of the dialkyl sulfide. Generally, higher reaction temperatures require a shorter reaction time and low boiling dialkyl sulfides require longer reaction times than high boiling dialkyl sulfides. For example, dimethyl sulfide requires a longer reaction time than the longer chain dialkyl sulfides. Times of reaction can easily be determined by one skilled in the art. Typical reaction times are between 1 and about 24 hours. Preferred reaction times are between about 2 and about 12 hours.
The products of the reaction are purified by conventional methods such as distillation, filtration, sublimation and extraction.
The identification of products is achieved by conventional methods such as elemental analysis, gas chromatography, refractive index and nuclear magnetic resonance (31 P-nmr and H-nmr).
Illustrative of the compounds which can be prepared by the method of the present invention are:
______________________________________
(CH.sub.3 S).sub.2 (C.sub.2 H.sub.5 S)P(S)
(CH.sub.3 S)(C.sub.2 H.sub.5 S).sub.2 P(S)
(C.sub.3 H.sub.7 S).sub.2 (CH.sub.3 S)P(S)
(C.sub.3 H.sub.7 S)(C.sub.2 H.sub.5 S).sub.2 P(S)
(CH.sub.3 S).sub.2 (C.sub.4 H.sub.9 S)P(S)
(CH.sub.3 S)(C.sub.4 H.sub.9 S).sub.2 P(S)
(C.sub.4 H.sub.9 S).sub.2 (C.sub.3 H.sub.7 S)P(S)
(C.sub.5 H.sub.11 S).sub.2 (CH.sub.3 S)P(S)
(CH.sub.3 S).sub.3 P(S)
(C.sub.2 H.sub.5 S).sub.3 P(S)
(C.sub.3 H.sub.7 S).sub.3 P(S)
(C.sub.4 H.sub.9 S).sub.3 P(S)
(C.sub.5 H.sub.11 S).sub.3 P(S)
(C.sub.8 H.sub.17 S).sub.3 P(S)
(C.sub.18 H.sub.37 S).sub.3 P(S)
##STR1##
##STR2##
##STR3##
______________________________________
the following examples are submitted to illustrate but not to limit the present invention.
6(ch.sub.3).sub.2 s+ p.sub.4 s.sub.10 → 4(ch.sub.3 s).sub.3 p(s)
in a 300 ml 316 stainless steel autoclave were placed 30 grams (CH3)2 S (0.48 mole) and 35.5 grams P4 S10 (0.08 mole). The autoclave was heated at 250° C. for 12 hours. After cooling, the pour out yield of liquid was 62.5 grams. The crude product was analyzed by mass spectra which showed the following components to be present:
(1) Major: (CH3 S)3 P(S)
(2) sub-major: (CH3 S)2 P(S)CH3
(3) minor:
(a) CS2,
(b) CH3 SSCH3,
(c) CH3 S3 CH3,
(d) CH3 SP(S) (CH3)2
(e) plus other minor components.
The crude product was distilled to give 13.5 grams product (b.p. 100°-105° C. at 0.3 mm) having the following assay by H-nmr:
(CH3 S)3 P(S): 82.9 mole %.
(CH3 S)2 P(S)CH3 : 17.1 mole %.
6(c.sub.2 h.sub.5).sub.2 s+ p.sub.4 s.sub.10 → 4(c.sub.2 h.sub.5 s).sub.3 p(s)
in a 300 ml stainless steel autoclave were placed 27 grams (C2 H5)2 S (0.3 mole) and 22.2 grams P4 S10 (0.05 mole). The autoclave was heated at 240° C. for 12 hours. The yield of crude product was 46 grams. Analysis by 31 P-nmr spectroscopy showed that the yield of (C2 H5 S)3 P(S) was 53.2% (Chemical Shift from H3 PO4 = -91.4 ppm. The crude product was distilled (b.p= 110°-175° at 0.1 mm Hg; nD 20 = 1.6169) to give 22 grams product (45% yield) which assayed 97% (C2 H5 S)3 P(S) by 31 P-nmr analysis.
6(c.sub.2 h.sub.5).sub.2 s+ p.sub.4 s.sub.10 →4(c.sub.2 h.sub.5 s).sub.3 ps
example II was repeated at a lower reaction temperature and in a glass Carius tube as follows:
In a 3 ml glass Carius tube were placed 1.19 grams (C2 H5)2 S (0.013 mole) and 0.97 grams P4 S10 (0.0022 mole). The tube was sealed and placed in an autoclave along with methyl alcohol to equalize the pressure in the Carius tube during heating. The autoclave was heated at 210°-220° for 12 hours. The product was analyzed by 31 P-nmr spectroscopy which showed only one major phosphorus component; (Chemical Shift from H3 PO4 = -92.1 ppm) (C2 H5 S)3 P(S) to be present in 88 mole % yield.
6(c.sub.2 h.sub.5).sub.2 s+ p.sub.4 s.sub.10 → 4(c.sub.2 h.sub.5 s).sub.3 ps
example III was repeated at shorter reaction times as follows:
On each of two 3 ml glass Carius tubes were placed 1.09 grams (C2 H5)2 S (0.012 mole) and 0.9 grams P4 S10 (0.002 mole. Each tube was sealed and placed in an autoclave along with methyl alcohol to equalize pressure and heated to 210° C. One tube was heated for 8 hours and the other tube for 1 hour. The products were analyzed by 31 P-nmr spectroscopy and gave the following results:
______________________________________
Heating Time
at 210° C.
Mole % (C.sub.2 H.sub.5 S).sub.3 P(S) (Chemical
Tube Hours Shift from H.sub.3 PO.sub.4 = -92.2 ± .1
______________________________________
ppm)
1 8 82
2 1 63
______________________________________
6(n-C.sub.4 H.sub.9).sub.2 S+ P.sub.4 S.sub.10 → 4(C.sub.4 H.sub.9 S).sub.3 P(S)
in a 300 ml stainless steel autoclave were placed 43 grams (n-C4 H9)2 S (0.29 mole) and 22 grams P4 S10 (0.049 mole). The autoclave was heated at 240° C. for 12 hours. The yield of crude product was 62 grams. The crude product was distilled to give 33.5 grams of product (bp=145°-180° C. at 0.1 mm Hg); nD 20 = 1.5822) which by 31 P-nmr analysis consisted of two major (C4 H9 S)3 P(S) components. These components are due to isomers of the --C4 H9 group present in (C4 H9 S)3 P(S).
6(n-C.sub.4 H.sub.9).sub.2 S= P.sub.4 S.sub.10 → 4(C.sub.4 H.sub.9 S).sub.3 P(S)
example V was repeated at a lower temperature and in a glass Carius tube as follows:
In a 3 ml glass Carius tube were placed 1.343 grams (n-C4 H9)2 S (0.009 mole) and 0.68 gram P4 S10 (0.0015 mole). The tube was sealed and placed in an autoclave along with methyl alcohol to equalize pressure and heated at 210°-220° C. for 12 hours. The crude product was analyzed by 31 P-nmr spectroscopy and gave the following results:
______________________________________
Chemical Shift from H.sub.3 PO.sub.4
Chemical
ppm Assignment Mole %
______________________________________
-103.5 Unknown 9.2
-102.7 Unknown 12.6
-93.5 (C.sub.4 H.sub.9 S).sub.3 P(S)
53.0
-91.9 Isomers of
(C.sub.4 H.sub.9 S).sub.3 P(S)
16.1
-90.4 Unknown 5.7
-78.9 Unknown 3.4
______________________________________
6(n-C.sub.8 H.sub.17).sub.2 S+ P.sub.4 S.sub.10 → 4(C.sub.8 H.sub.17 S).sub.3 P(S)
in a 3 ml glass Carius tube were placed 1.349 grams (n-C8 H17)2 S (0.00523 mole) and 0.414 grams P4 S10 (0.009 mole). The sealed tube was placed in an autoclave and heated at 210°-220° C. for 12 hours. The product was analyzed by 31 P-nmr spectroscopy and gave the following results:
______________________________________
Chemical Shift from H.sub.3 PO.sub.4
Compound
ppm Assignment Mole %
______________________________________
-93.6 (C.sub.8 H.sub.17 S).sub.3 P(S)
75
-91.9 Isomers of
(C.sub.8 H.sub.17 S).sub.3 P(S)
12.5
-90.4 Isomers of
(C.sub.8 H.sub.17 S).sub.3 P(S)
12.5
______________________________________
6(n-C.sub.8 H.sub.17).sub.2 S+ P.sub.4 S.sub.10 → 4(C.sub.8 H.sub.17 S).sub.3 P(S)
example VII was repeated at atmospheric pressure as follows:
In a 25 ml 3-neck pyrex reaction flask provided with a reflux condenser, thermometer and sampling dip tube were placed, while stirring with a magnetic bar, 13.9 grams (n-C8 H17)2 S (0.0539 mole) and 3.99 grams P4 S10 (0.00898 mole). The reaction was kept under an atmosphere of nitrogen while heating at 220° C. Samples were removed during the reaction and analyzed by 31 P-nmr spectroscopy.
______________________________________
Hours
Heated Mole % (C.sub.8 H.sub.17 S).sub.3 P(S)
at 220° C.
(Chemical Shift from H.sub.3 PO.sub.4 = -92.4 + 0.2
______________________________________
ppm)
1 19
1.5 27.5
2.0 31.0
5.0 40.0
______________________________________
There were 10 other phosphorus products present after heating at 220° C. for 5 hours as shown by the 31 P-nmr spectra.
6c.sub.4 h.sub.9 sch.sub.3 + p.sub.4 s.sub.10 → (ch.sub.3 s).sub.3 p(s) p(s)+ (ch.sub.3 s).sub.2 (c.sub.4 h.sub.9 s)p(s)+ (c.sub.4 h.sub.9 s).sub.3 p(s)
in a 3 ml glass Carius tube were placed 1.25 grams C4 H9 SCH3 (0.012 moles) and 0.89 grams P4 S10 (0.002 moles). After sealing, the tube was placed in an autoclave along with methyl alcohol to equalize pressure and heated to 210° C. for 6 hours. The product was analyzed by 31 P-nmr spectroscopy which gave the following results.
______________________________________
Chemical Shift
from H.sub.3 PO.sub.4
Compound
ppm Assignment Mole %
______________________________________
-98.9 Unknown 9.8
-98.3 Unknown 3.3
-97.3 (CH.sub.3 S).sub.3 P(S)
27.7
-96.2 Unknown 6.0
-95.2 Mixed (CH.sub.3 S).sub.2 (C.sub.4 H.sub.9 S)P(S)
and
(CH.sub.3 S)(C.sub.4 H.sub.9 S).sub.2 P(S)
32.6
-94.5 Unknown 6.0
-93.5 (C.sub.4 H.sub.9 S).sub.3 P(S)
14.7
______________________________________
The present invention is defined in the following claims.
Claims (5)
1. A method of preparing compounds of the formula:
(R.sup.1 S).sub.x (R.sup.2 S).sub.y P(S) (I)
wherein x+ y= 3; R1 and R2 are the same or different and are selected from the group consisting of C1 -C18 straight-chain or branched alkyl and cycloalkyl of 5 to 6 carbons in the ring and the C1 -C4 alkyl substituted derivatives thereof; comprising contacting under at least an autogenous pressure at a temperature of from about 150° C. to 300° C. a reactant selected from the group consisting of dialkyl sulfide reactants of the formula:
R.sup.1 SR.sup.2 II
wherein R1 and R2 are as defined above with a phosphorus pentasulfide reactant of the formula:
P.sub.4 S.sub.10.
2. The method of claim 1 wherein R1 and R2 are the same or different and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertbutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl and ethylcyclohexyl.
3. The method of claim 1 wherein R1 and R2 are the same and are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl and ethylcyclohexyl.
4. The method of claim 1 wherein said autogenous pressure is between about 1 and about 300 atmospheres.
5. The method of claim 1 wherein said reactants are employed in stoichiometric amounts according to the following equation:
6R.sup.1 SR.sup.2 + P.sub.4 S.sub.10 → 4(R.sup.1 S).sub.x (R.sup.2 S).sub.y P(S)
wherein x, y, R1 and R2 are as defined in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/650,488 US4034024A (en) | 1974-10-15 | 1976-01-19 | Method of preparing trialkyl tetrathiophosphates |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51452574A | 1974-10-15 | 1974-10-15 | |
| US05/650,488 US4034024A (en) | 1974-10-15 | 1976-01-19 | Method of preparing trialkyl tetrathiophosphates |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US51452574A Continuation | 1974-10-15 | 1974-10-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4034024A true US4034024A (en) | 1977-07-05 |
Family
ID=27058231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/650,488 Expired - Lifetime US4034024A (en) | 1974-10-15 | 1976-01-19 | Method of preparing trialkyl tetrathiophosphates |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4034024A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133830A (en) * | 1977-02-04 | 1979-01-09 | Stauffer Chemical Company | Process for preparing alkyl or aryl thiophosphorus halides and mixed isomers thereof |
| CN107955034A (en) * | 2017-10-25 | 2018-04-24 | 江苏腾龙生物药业有限公司 | A kind of preparation process of Rogor active compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328360A (en) * | 1962-07-06 | 1967-06-27 | Exxon Research Engineering Co | Polymers containing phosphorus |
| US3487131A (en) * | 1967-02-27 | 1969-12-30 | Ethyl Corp | Process for making tetrathiophosphates |
-
1976
- 1976-01-19 US US05/650,488 patent/US4034024A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328360A (en) * | 1962-07-06 | 1967-06-27 | Exxon Research Engineering Co | Polymers containing phosphorus |
| US3487131A (en) * | 1967-02-27 | 1969-12-30 | Ethyl Corp | Process for making tetrathiophosphates |
Non-Patent Citations (1)
| Title |
|---|
| Houben-Weyl, Methoden der Organischen Chemie, vol. 12/2 (1964), p. 747. * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133830A (en) * | 1977-02-04 | 1979-01-09 | Stauffer Chemical Company | Process for preparing alkyl or aryl thiophosphorus halides and mixed isomers thereof |
| CN107955034A (en) * | 2017-10-25 | 2018-04-24 | 江苏腾龙生物药业有限公司 | A kind of preparation process of Rogor active compound |
| CN107955034B (en) * | 2017-10-25 | 2020-05-12 | 江苏腾龙生物药业有限公司 | Preparation process of raw dimethoate |
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